The present application is a continuation-in-part of our prior co-pending related application U.S. application Ser. No. 09/670,159 filed Sep. 26, 2000, which is hereby incorporated by reference in its entirety.
The invention relates to an isomerization process involving an adsorptive separation process and an innovative fractional distillation method which reduces the cost of recovering desorbent from the effluent streams of the continuous adsorptive separation process.
In many commercially important petrochemical and petroleum industry processes it is desired to separate closely boiling chemical compounds or to perform a separation of chemical compounds by structural class. It is very difficult or impossible to do this by conventional fractional distillation due to the requirement of numerous columns or excessive amounts of energy. The relevant industries have responded to this problem by utilizing other separatory methods which are capable of performing a separation based upon chemical structure or characteristics. Adsorptive separation is such a method and is widely used to perform these separations.
In the practice of adsorptive separation a feed mixture comprising two or more compounds of different skeletal structure is passed through one or more beds of an adsorbent which selectively adsorbs a compound of one skeletal structure while permitting other components of the feed stream to pass through the adsorption zone in an unchanged condition. The flow of the feed through the dsorbent bed is stopped and the adsorption zone is then flushed to remove nonadsorbed materials surrounding the adsorbent. Thereafter the desired compound is desorbed from the adsorbent by passing a desorbent stream through the adsorbent bed. The desorbent material is commonly also used to flush nonadsorbed materials from the void spaces around and within the adsorbent. This could be performed in a single large bed of adsorbent or in several parallel beds on a swing bed basis. However, it has been found that simulated moving bed adsorptive separation provides several advantages such as high purity and recovery. Therefore, many commercial scale petrochemical separations especially for specific paraffins and xylenes are performed using simulated countercurrent moving bed (SMB) technology.
A description of the use of simulated moving bed (SMB) adsorptive separation to recover paraffins from a kerosene boiling range petroleum fraction is provided in the contents of a presentation made by R. C. Schulz et al. at the 2nd World Conference on Detergents in Montreux, Switzerland on Oct. 5-10, 1986. This shows several incidental steps in the process such as fractionation and hydrotreating. A more detailed overall flow scheme for the production of olefins from the kerosene derived paraffins is presented in U.S. Pat. No. 5,300,715 issued to B. V. Vora.
Several economic advantages are derived from the continuous, as compared to batch-wise, operation of large-scale adsorptive separation processes. Recognition of this has driven the development of simulated moving bed (SMB) adsorptive separation processes. These processes typically employ a rotary valve and a plurality of lines to simulate the countercurrent movement of an adsorbent bed through adsorption and desorption zones. This is depicted, for instance, in U.S. Pat. No. 3,205,166 to D. M. Ludlow, et al. and U.S. Pat. No. 3,201,491 to L.O. Stine et al.
U.S. Pat. No. 3,510,423 to R. W. Neuzil et al. provides a depiction of the customary manner of handling the raffinate and extract streams removed from an SMB process, with the desorbent being recovered, combined and recycled to the adsorption zone. U.S. Pat. No. 4,036,745 describes the use of dual desorbent components with a single adsorption zone to provide a higher purity paraffin extract. U.S. Pat. No. 4,006,197 to H. J. Bieser extends this teaching on desorbent recycling to three component desorbent mixtures.
U.S. Pat. No. 5,177,295 issued to A. R. Oroskar et al. describes the fractionation of a xe2x80x9cheavyxe2x80x9d desorbent used in the recovery of paraxylene from a mixture of aromatic hydrocarbons.
The dividing wall or Petyluk configuration for fractionation columns was initially introduced some 50 years ago by Petyluk et al. A recent commercialization of a fractionation column employing this technique prompted more recent investigations as described in the article appearing at page 14 of a supplement to The Chemical Engineer, Aug. 27,1992.
The use of dividing wall columns in the separation of hydrocarbons is also described in the patent literature. For instance, U.S. Pat. No. 2,471,134 issued to R. O. Wright describes the use of a dividing wall column in the separation of light hydrocarbons ranging from methane to butane. U.S. Pat. No. 4,230,533 issued to V. A. Giroux describes a control system for a dividing wall column and illustrates the use of the control system in the separation of aromatics comprising benzene, toluene and ortho-xylene.
The invention is an improved isomerization process involving a simulated moving bed adsorptive separation process characterized by the use of an integrated fractional distillation column to recover both the extract and raffinate products of the adsorptive separation and the desorbent in a single fractionation column. A portion of the column is divided into parallel fractionation zones with one receiving the raffinate stream and the other receiving the extract stream of the adsorptive separation zone. The desorbent in these streams is rejected into a common portion of the column for further purification. This reduces the capital and operating costs of the required separation and thus of the adsorption process.
One broad embodiment of the invention may be characterized as an isomerization process where the isomerization zone effluent is passed to a simulated moving bed adsorptive separation process comprising a bed of a selective adsorbent maintained at adsorption promoting conditions. The normal pentane and normal hexane are selectively retained on a quantity of the selective adsorbent, thus forming a raffinate stream comprising the isomerized products and the desorbent formerly present in the quantity of the selective adsorbent. The desorbent is contacted with the quantity of the selective adsorbent which has retained the normal alkanes under desorption promoting conditions to yield an extract stream comprising the normal alkanes and the desorbent compound. The extract stream is passed into a fractionation column operated at fractionation conditions and divided into at least a first and a second vertical fractionation zone, with each zone having an upper and a lower end located within the fractionation column, with the first and second fractionation zones being in open communication at their upper ends at a first end of the column and with the extract stream entering the fractionation column at an intermediate point of the first fractionation zone. The raffinate stream is passed into an intermediate point of the second fractionation zone of the fractionation column. An extract product stream is removed from a first end of the first fractionation zone and contains the normal alkanes, the first end not being in communication with the second fractionation zone and being located at the second end of the column. A raffinate product stream is removed from a first end of the second fractionation zone and contains the isomerized products, the first end not being in communication with the first fractionation zone. A desorbent stream is removed from the first end of the fractionation column.